Process and catalyst for hydrochlorination of hydrocarbons

ABSTRACT

Methyl chloride is produced by contacting methanol and hydrogen chloride in the vapor phase in the presence of KZnCl 3  supported on silica. The process produces methyl chloride in good yield with minimal formation of dimethyl ether as a by-product.

BACKGROUND OF THE INVENTION

This invention relates to catalytic hydrochlorination processes. Inparticular, the invention relates to the catalytic hydrochlorination ofhydrocarbyl compounds.

Chlorinated hydrocarbons have various utilities as industrial chemicalsand solvents. For example, methyl chloride is useful as a catalystcarrier in low temperature polymerizations as a fluid for thermometricand thermostatic equipment: as a methylating agent in organic synthesis,such as of methylcellulose: in the preparation of silicone rubbers; andas an extractant and low temperature solvent.

Methods for the production of chlorinated hydrocarbons, such as methylchloride, are well-known. In a typical method for the production ofmethyl chloride, vaporized methanol and hydrogen chloride are mixed inapproximately equimolar proportions and passed through a converterpacked with a catalyst such as alumina gel or zinc chloride on activatedcarbon to form methyl chloride. Other known methods involve reactions inthe liquid phase using an aqueous solution of catalyst. For example,U.S. Pat. No. 4,073,816 teaches that monochloroalkanes ormonochlorocycloalkanes can be prepared by reacting an alcohol withhydrogen chloride in the presence of aqueous zinc chloride. GermanOffensive 3332253 teaches that mixtures containing alcohols and ethersmay be converted to alkyl halides by reactions with hydrogen chloride inthe presence of an aluminum-zinc chloride catalyst. This referencefurther teaches that small amounts of alkali metal chlorides and largeramounts of cadmium, iron and/or magnesium chlorides may be added withthe zinc chloride to increase the efficiency of the catalyst.

Such methods do not resolve all the existing problems. The problemsrelating to the manufacture of chlorinated hydrocarbons includeexcessive production of by-products: requirements for use of excesshydrochloric acid and excessive coking of the catalyst. An additionalproblem related to the use of alumina or alumina supported catalysts isthe breakdown of the alumina to produce bohemite. What is needed is anon-alumina catalyst which results in a high yield of chlorinatedhydrocarbon: which permits the complete conversion of hydrochloric acid;which does not experience excessive coke formation: and which reducesthe amount of by-products formed.

SUMMARY OF THE INVENTION

In one aspect, the present invention is such a hydrochlorinationcatalyst comprising a Group IA cation, ion, a Group IIA or IIB cationand a neutralizing number of counter anions supported on a non-aluminaporous carrier. The molar ratio of the Group IA cation to the Group IIAor IIB cation is at least about 0.5:1 and no greater than about 1.5:1.

In a second aspect, the present invention is a process for thehydrochlorination of hydrocarbyl compounds to form chlorinatedhydrocarbyl compounds wherein the hydrocarbyl compounds and hydrogenchloride are contacted in the vapor phase in the presence of thecatalyst described above under reaction conditions sufficient to formthe chlorinated hydrocarbyl compounds.

The chlorinated hydrocarbyl compounds produced by the practice havevarious utilities as industrial chemicals and solvents. Methyl chloride,for example, is useful as a catalyst carrier in low temperaturepolymerizations: as a fluid for thermometric and thermostatic equipment:as a methylating agent in organic synthesis, such as of methylcellulose;and as an extractant and low temperature solvent.

It is surprising that the use of a catalyst supported on a non-aluminasupport and comprising the specified molar ratio of the cationsdescribed above results in a high yield of chlorinated hydrocarbylcompounds with reduced formation of by-products and with minimal cokingof the catalyst. The use of the specified non-alumina supported catalysteliminates the problem of bohemite formation while maintaining highyields.

DETAILED DESCRIPTION OF THE INVENTION

The catalyst of the present invention is advantageously a salt of aGroup IA metal (alkali metal): a Group IIA or IIB, preferably Group IIB,metal: and a neutralizing number of counter anions supported on anon-alumina porous carrier material. Preferred Group IA metals includesodium, potassium, rubidium, lithium and cesium, with potassium andcesium being more preferred and potassium being most preferred. Thepreferred Group IIB metals include zinc, cadmium and mercury with zincbeing more preferred. While any counter anion, such as bromide, chlorideand fluoride, is suitable in the catalyst of this invention, the halidesare preferred with chloride being most preferred. Other suitable anionsare nitrates, sulfate, phosphate, acetates, oxylate and cyanides.

The molar ratio of Group IA metal to Group IIA or IIB metal in the saltis preferably at least about 0.5:1 and no greater than about 1.5:1. Itis more preferred that the molar ratio is at least about 0.9:1 and nogreater than about 1.1:1 and most preferred that approximately equimolarportions of the two metals are used. The amount of counter anion used isthat which is sufficient to neutralize the cations of the salt.

Any non-alumina support which will withstand the hydrochlorinationconditions described herein can be used in the process of the presentinvention. Examples of appropriate supports include the well-knowncarbon supports such as activated carbon, carbon black, chars and coke.Other suitable supports that may be used to support the catalyst includepumice, silica gel, asbestos, diatomaceous earth, fullers earth,titania, zirconia, magnesia, magnesium silicate, silicon carbide,silicalite, and silica. A preferred support is silica. A silica having asurface area between 100 m² /g and 300 m² /g and a pore volume in therange of 0.75 cc/ to 1.4 cc/g is particularly active in the process ofthis invention.

The salt is suitably supported on the carrier material by any standardimpregnation technique such as that disclosed in Experimental Methods inCatalytic Research, Vol. II, edited by R. B. Anderson and P. T. Dawson,Academic Press, New York, 1978. A solution of both the Group IA andGroup IIA or IIB metal cations and the associated anions may be employedto impregnate the support material or the metal salts may be impregnatedfrom separate solutions. The resulting catalyst comprising thecatalytically active salt and the support preferably comprises fromabout 1 to about 50 weight percent of the Group IIA or IIB metal salt,e.g., ZnCl₂, and from about 0.5 to about 30 weight percent of the GroupIA metal salt, e.g., KCl, based on the percentage by weight of the totalsalts to the support. It is preferred to use at least about 20 and nogreater than about 30 weight percent of the Group IIA or IIB metal saltand at least about 10 and no greater than about 20 weight percent of theGroup IA metal salt and more preferred to use about 20 weight percent ofthe Group IIA or IIB metal salt and about 10 weight percent of the GroupIIA metal salt. Preferred weight percents of the two salts are selectedso as to result in approximately equimolar proportions of the Group IAand Group IIA or IIB salt being used.

The process of the present invention comprises contacting a alcohol andhydrogen chloride in the presence of the aforementioned catalyst underreaction conditions sufficient to produce the corresponding chlorinatedhydrocarbon. Examples of alcohols useful in the practice of thisinvention include compounds corresponding to the formula

    ROH

wherein R is alkyl, aryl, arylalkyl and alkylaryl. It is preferred thatR is alkyl and more preferred that R is lower alkyl having from about 1to about 5 carbon atoms. It is most preferred that R is alkyl havingfrom 1 to about 3 carbon atoms. Examples of preferred alcohol compoundsthus include methanol, ethanol and propanol with methanol being morepreferred.

Molar ratios of alcohol to hydrogen chloride useful in the practice ofthis invention are generally at least about 1:10 and no greater thanabout 10:1. When hydrogen chloride is used in excess, it is preferredthat the amount of excess hydrogen chloride is no more than about 30molar percent. It is preferred that the alcohol be used in excess. Whenthe alcohol is used in excess, it is preferred that the molar ratio ofalcohol to hydrogen chloride is about no greater than about 2:1 and morepreferred that it is no greater than about 1.5:1 and most preferred thatis is about 1.1:1.

The temperature range useful in the practice of this invention is any atwhich the hydrochlorination reaction will proceed. Preferably, thereaction is conducted at a temperature of at least about 25° C. and nogreater than about 475° C. with at least about 175° C. to no greaterthan about 300° C. being more preferred. The most preferred temperatureranges from at least about 250° C. to no greater than about 275° C.Pressures typically employed in the process of the present invention areat least about 14 psig and no greater than about 500 psig. Preferredpressures are at least about 35 psig and no greater than about 150 psig.

Gas hourly space velocities are suitably at least about 100 and nogreater than about 10,000 hours⁻¹, preferably at least about 300 and nogreater than about 3000 h⁻¹.

The process may be operated in a batch mode or continuously althoughcontinuous operation is preferred. In a preferred embodiment, vaporizedmethanol and hydrogen chloride are added in approximately equimolarproportions to a fixed bed reactor containing a KZnCl₃ catalystsupported on silica. The resultant products are separated bydistillation.

The process of this invention is effective in reducing the amount ofby-products formed. In a preferred embodiment wherein methanol andhydrogen chloride react to form methyl chloride, the production ofby-products such as dimethyl ether is decreased. The process of thepresent invention also results in a long-lived catalyst. The catalyst ofthe present invention is stable and the absence of alumina eliminatesthe problem of bohemite formation.

ILLUSTRATIVE EMBODIMENTS

The following examples are provided to illustrate the invention andshould not be interpreted as limiting it in any way. Unless statedotherwise, all parts and percentages are by weight.

EXAMPLE 1 --CATALYST PREPARATION

A silica sample is sieved between three screens and the fractionsretained by 4 mesh, 5 mesh and 8 mesh, respectively, are collected. The8 mesh fraction is used in the preparation of 200 g samples of about 500cubic centimeters each. A 200 g sample is placed in a 2 liter dish anddried 48 hours at 150° C. The sample is transferred to 1 liter flutedflask, placed on a rotovap and cooled to 70° C. under vacuum. The silicais then impregnated with a solution of 60 g of ZnCl₂ and 32.81 g of KClin a total volume of 278 cubic centimeters of water. The impregnatedcatalyst is returned to the 2 liter dish and air dried for 24 hours andthen dried for an additional 25 hours at 150° C.

EXAMPLE 2

A three-liter portion of catalyst, prepared as described above, isplaced into an Inconel reactor that is 20 feet long and 1.25 inches indiameter. The reactor is then purged with nitrogen for 48 hours at 220°C. The catalyst is then conditioned with HCl mixed with nitrogen priorto reaction with methanol. The proportions of methanol to hydrogenchloride and the reaction temperature are varied as shown in Table Ibelow. The reactor effluent is analyzed by gas chromatography todetermine the conversion obtained and the amount of dimethyl etherproduced relative to the amount of methyl chloride produced. The resultsobtained are shown in Table I below.

                  TABLE I                                                         ______________________________________                                                                      Con-                                                  Methanol HCl     Temp   version.sup. ○1                                                               DME/MC.sup. ○2                    Run   (lb/hr)  (lb/hr) (°C.)                                                                         (%)    (ppm)                                    ______________________________________                                        1     8.00     10.00   220    96.6   11726                                    2     8.00     10.00   235    96.4   11545                                    3     3.92     5.57    220    99.0    6981                                    4     3.92     4.91    220    98.2    8957                                    5     7.46     10.57   220    98.4    7713                                    6     5.83     7.78    220    98.4    8161                                    7     8.00     10.00   220    93.1   13780                                    8     4.14     4.95    220    94.3   13441                                    9     8.00     10.00   220    93.4   14065                                    10    4.24     4.84    220    91.3   16209                                    11    9.81     10.34   220    93.6   13900                                    ______________________________________                                         .sup. ○1 Conversion of methanol to methyl chloride                     .sup. ○2 Parts of dimethyl ether produced per million parts of         methyl chloride                                                          

The data above illustrate that the use of the catalytic process of thisinvention results in a high rate of conversion of methanol. Runs 1 and 2demonstrate that an increase in the reaction temperature from 220° C. to235° C. has little effect on conversion or dimethyl ether production.Runs 3 and 4 demonstrate the effect of varying the ratio of methanol tohydrogen chloride. Run 3 represents a 25 percent molar excess ofhydrogen chloride while Run 4 shows a 10 percent molar excess. At the 10percent excess level, the conversion decreases and the dimethyl etherproduction increases although in either case the conversion is high andthe dimethyl ether production is low. Runs 8, 10 and 11 show the effectof decreasing the molar proportion of HCl until methanol is used inexcess. The ratios of methanol to HCl change from 1:1.05 in Run 8 to 1:1in Run 10 and to 1.13:1 and follow the trend shown in Runs 3 and 4.These trends indicate that high conversion and acceptably low dimethylether production may be obtained when methanol is used in excess. Runs1, 7 and 9 are all identical and demonstrate that after a breaking inperiod, the catalyst is stable within the time frame of the experiment.

What is claimed is:
 1. A process for the hydrochlorination of alkanolscorresponding to the formula

    ROH

wherein R is alkyl, to form chlorinated compounds comprising contactingthe alkanol and hydrogen chloride at a molar ratio of at least about1:10 and no greater than about 10:1 in the vapor phase in the presenceof a hydrochlorination catalyst, said catalyst comprising a first cationselected from the group consisting of potassium, cesium, sodium,rubidium and lithium and a second cation selected from the groupconsisting of zinc, cadmium and mercury in a molar ratio of first cationto second cation of at least about 0.5:1 and no greater than about 1.5:1and a neutralizing number of counter anions supported on a non-aluminaporous carrier under reaction conditions sufficient to form thechlorinated compounds corresponding to the starting alkanols.
 2. Theprocess of claim 1 wherein the alkanol is a lower alkanol.
 3. Theprocess of claim 1 wherein the lower alkanol is methanol.
 4. The processof claim 3 wherein the molar ratio of methanol to hydrogen chloride isat least about 1.1:1 and no greater than about 2:1.
 5. The process ofclaim 4 wherein the molar ratio of methanol to hydrogen chloride is atleast about 1.1:1 and no greater than about 1.5:1.
 6. The process ofclaim 1 wherein the reaction temperature is at least about 175° C. andno greater than about 300° C.
 7. The process of claim 6 wherein thereaction temperature is at least about 250° C. and no greater than about275° C.
 8. The process of claim 1 wherein the reaction pressure is atleast about 35 psig and no greater than about 150 psig.
 9. The processof claim 10 wherein the first cation of the catalyst is a cation of ametal selected from the group consisting of potassium and cesium. 10.The process of claim 26 wherein the second cation of the catalyst is azinc cation.
 11. The process of claim 10 wherein the counter ion of thecatalyst is chloride.
 12. The process of claim 11 wherein the ratio ofpotassium to zinc is at least about 0.9:1 and no greater than about1.1:1.
 13. The process of claim 12 wherein the ratio of potassium tozinc is about 1:1.
 14. The process of claim 13 wherein the catalyst isKCl and ZnCl₂ supported on silica having a surface area between 100 m²/g and 300 m² /g and a pore volume in the range of 0.75 of 0.75 cc/g to1.4 cc/g.
 15. The process of claim 14 wherein methanol and hydrogenchloride are contacted in the vapor phase at a temperature of about 250°C. in the presence of a catalyst comprising KCl and ZnCl₂ supported onsilica under reaction conditions sufficient to produce methyl chloride.16. The process of claim 9 wherein the first cation of the catalyst ispotassium.
 17. The process of claim 3 wherein the molar ratio ofmethanol to hydrogen chloride ranges from 1.131 to 1:1.05.